Vat dyestutfs of the anthraqxtinone series



Patented Oct. 4, 1932 p UNETED STATES GEORG RGSCH, OF COLOGNE-MULHEI M,GERMANY, ASSIGNOR TO we Frrcs WORKS, INC., OF NEW YORK, N. Y., ACORPORATION OF DELAYVARE VAT DYESTUIEFS or THE AnrHaAooInonE snares NoDrawing. Application filed July 28, 1930, Serial No. 471,424, in GermanyJuly 30,1929.

The present invention relates to a process of manufacturing vatdyestufis of the anthraquinone series and to new products obtainable bysaid process.

In accordance with the invention new vat dyestuffs of the anthraquinoneseries are obtainable by converting phenylene or napthyl ene-di (1thioanthraquinone 2 -carboxylic acids) each possessing a free orthoposition to the sulfur in the benzeneor naphthalene nucleus andanswering the general formula:

HOOG COOH S-phenylene-S- (naphthylene) wheren the phenylene ornaphthalene nucleus may be substituted by monovalent substituents, intodithioxanthones of the general formula:

in which R signifies a benzene or naphthalene nucleus which may besubstituted by monovalent substituents, such as halogen atoms, alkoxygroups or the like.

The condensation can be effected by means of acid condensing agents,that is to say, substances which are either acids or which form acidswith water, as for example, by heating with phosphorus penthachloride ina solvent like nitrobenzene with or without the addition-of a littleconcentrated sulfuric acid or by heating with concentrated sulfuric acidalone. The phenylene or naphthylene-di ('l-thioanthraquinone 2 'C2Lll3OXyliC acids) canbe obtained by causing 1-chloro-anthraquinone-2-carboxylic acidsor l-diazo-an thra-quinone-2-carboxylic acidsto act endimercaptans of the benzene or naphthalene Ewample 1 57.3 partsby weight of 1-chloroanthraquinone-2-carboxylic acid, 19.2 parts byweight of naphthalene-1,6-dimercaptanand 25 parts by Weight of causticalkali dissolved in 400 parts by weight of water are heated to boilingunder reflux for 8 hours. The reaction mixture solidifies oncooling toand crystalline magma. The product is dissolved with boiling water,filtered and-the dipotassium GENERAL ANILINE salt of the formeddicarbo'xylic acid is separated by the addition of .common'salt and thenfiltered. The productisfonce again dlssolved in boiling water, acidifiedwith acetlc acid,the orange colored dicarboxylic acid is filtered bysuction, washed with water and dried. The yield amounts to 65 parts byweight.

The product can be recrystallized from a 5 large quantity ofnitrobenzene or from acetic anhydridc. It dissolves in. concentratedsulfuric acid. to give first a violet black. coloration, which thenchanges to orange.

69,2 parts by weight of the dicarboxylic acid (a), 680 parts by weightof nitrobenzene and 41,? parts by weight of phosphorus pentachloride areheated to boiling for about half an hour, whereby the dithioxanthoneseparates as an orange colored precipitate. After cooling the sameisfiltered by suction, washed 40 with a little nitrobenzene and ether anddried. The yield amounts to 65 parts by weight. The dyestufi' dissolvesin concentrated sulfuric acid with an orange coloration and yields oncotton from a blue hydrosulfite vat a very clear orange after.oxidation.

Ewam-ple o a 7 57.3 parts by weight-of 1-chloroanthraquin.

one-2-carboxylic acid, 19.2 parts by weight ofnaphthalene-2.6-dimercaptan and 25 parts by weight of causticalkalidissolved in 400 parts by weight of water are caused to react in exactlythe same manner as described in Example 1 (a). An orange coloredsubstance. is obtained in a yield of parts by weight. The dicarboxylicacid dissolves in concentrated sulfuric acid first with a Violetcoloration which then changes into reddishorange.

69.2 parts by weight of the dicarboxylic acid 2 (a), 680' parts byweight of nitrobenzene and 41,7 parts by weight of phosphoruspentachlo'ride are caused to react in exactly the same manner asdescribed in Example 1 The resulting dithioxanthone is obtained as anorange-colored substance in a yield of 65 parts by weight. The dyestuffdissolves in concentrated sulfuric acid with a reddish-orange colorationand dyes cotton from a blue hydrosulfite vat a very clear reddish-orangeafter oxidation.

Ewample 3 57.3 parts by weightof l-chl'oroanthraquinone-Q-carboxylicacid, 19.52 parts by weight of naphthalene-2.7-dimercaptan and 25pa-rtsby weight of caustic alkali dissolved in: 400 parts by weight of waterare caused to re act in exactly-the same manner as described in Example1 (a); An orange colored sub stance is obtained in a yield of 72 partsby: weight The dicarboxylic acid dissolves on of meta phenylenedimercaptan and parts heating in concentrated sulfuric acid with 25parts by weight of the dicarboxylic acid a reddish-Violet C 1Ora i n- I4 (a) are dissolved in 500 parts by volume (6) of hot acetic anhydride,9 parts by Weight I of condentrated sulfuric acid are added and heatingto boiling is efiected for half an hour. The resulting product is thenfiltered by suc- 0 S S O tion while. hot and washed with glacial aceticI I acid in ether; the dithioxanthone is obtained as an orange coloredpowder which dissolves in concentrated sulfuric acid with an orangecoloration and yields on cotton from a violet hydrosulfite vat ayellowish orange shade after'oxidation.

Similar dyestuffs have been obtained from1-chloroanthraquinone-2-carboxylic acid as the one component andcompounds of the following formula as the second component.

69.2 arts by weight of the dicarboxylic acid 3 (ad 680 parts by weightof nitrobenzene and 41,7 parts by Weight of phosphorus pentachloride arecaused to react in exactl the same manneras in Example 1 The resultingdithioxanthone is a brown substance, which dissolves in concentratedsul-.

h a red coloration and yields furic acid wit Component Y Properties ofthe dyestutf on cotton from a green hydrosulfite vat a 1 vbrownish-yellow shade after oxidation. It V should be pointed out thatrlng closure to- (1) P gggggg g gggg gg gggfi wards the naphthalenenucleus may also n ra i h yein cotton from a green alkaline hydroproceed1n a manner different from that msulfite vat red-orange shades. (heatedin the above formula. The yield amounts to 62 parts by weight. 7

Example 4 HS (2) SH Orange powder, soluble in strong I sulfuric acidwith a reddishbrown coloration, dyeing cotton from a green alkaline 0hydrosulfite vat yellow-orange shades fast to exposure and light.

o s S o VT SH OOH H000 (3). 7 Fl Orange colored powder, dyeing 114 partsby weight of l-chloroanthraquing ggg vatreddlsh'bmwn one-2-carboxylicacid 28.4 parts by weight by weight of caustic alkali dissolved in 400parts by weight of Water are caused to react in exactly the same manneras described in Example 1 (a). orange colored sub stance is obtained ina yield of 130 parts by weight. The dicarboxylic acid dissolves inconcentrated sulfuric acid with a blueishred coloration.

(obtainable from 1.5-naphthylcne diamino-3.7-disulfonic acid bySandmeyers reaction and converting the SOsH groups into SH groupsaccording to known methods.)

Dyes cotton from an olive col- -ored vat yellowish-brown shades.

(obtainable by treating 2.6-dimercaptonaphthylene with chlorine inchlorobenzene and reduc- O tion of the disulfide being firstly g gformed with Zn and H01.)

cotton from a green alkaline co co I V v i I claim 1. The compoundsformula:

of the" probable wherein R means a benzene or naphthalene nucleus whichmay be substituted by halogen atoms, said compounds forming goldenyellowto red-orange powders, soluble in strong sulfuric acid with orange tored colorations, dyeing cot-ton from a violet to green hydrosulfite vatorange to brownish-red. shades of good fastness properties.

said compounds forming golden-yellow to red-orange powders, soluble instrong sulfuric acid With orange to red colorations, dyeing cotton froma violet to green hydrosulfite vat orange to brownish-red shades of goodfastness properties.

3. The compound of the probable formula:

' said compound dissolving in strong sulfuric acid with an orangecoloration, dyeing cotton from a blue alkaline hydrosulfite vat clearorange shades.

In testimony whereoLI aflin my signature.

GEORG BOSCH.

